Modulations of electronic states in plasmonic strong coupling systems and their application to photochemical reaction fields

• Project Area: Application of Cooperative-Excitation into Innovative Molecular Systems with High-Order Photo-functions
• Project/Area Number: 17H05245
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Hokkaido University
• Principal Investigator: 上野 貢生 北海道大学, 電子科学研究所, 准教授 (00431346)
• Project Period (FY): 2017-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥7,930,000 (Direct Cost: ¥6,100,000、Indirect Cost: ¥1,830,000); Fiscal Year 2018: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2017: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
• Keywords: 振動モード強結合 / 電子状態変調 / 光増強場 / 励起状態ダイナミクス / プラズモン共鳴 / 光物性 / ナノ材料 / 励起状態変調 / プラズモン / 強結合

Outline of Annual Research Achievements

分子振動モードとプラズモンモードとの強結合が分子の振動状態だけではなく、電子状態にまで影響を及ぼすことを明らかにするために、平成30年度は赤外の幅広い波長域において高い光電場増強効果を示す金属ナノ構造体の構造設計を明らかにした。まず、可視波長域において光ナノ共振器と金ナノ微粒子のプラズモン共鳴がモード強結合を示して、幅広い波長において高い光吸収と光電場増強効果を示すことを明らかにした。特筆すべき点は、プラズモンの位相緩和時間が、モード強結合に基づくプラズモン状態の変調により変化することを明らかにした点である。この可視域におけるモード強結合の原理を利用して、赤外域に共鳴を示す構造設計に展開した。石英基板上に厚さ100 nmの金フィルムを成膜し、その上に厚さ450 nmの酸化チタン層を成膜することで、2400cm-1に共振を示すファブリ・ペロー共振器を構築した。その上に電子ビームリソグラフィー／リフトオフ法により赤外に波長選択的にプラズモン共鳴を示す金ナノチェイン構造を作製したところ、2000～4000cm-1においてモード強結合によりスペクトルが分裂する現象が観測された。また、金ナノチェイン構造の長さにより共鳴波長を変化させたところ、共鳴効率の増大により顕著に赤外光の吸収効率が増大することを吸収スペクトル測定から明らかにした。つまり、赤外の幅広い波長域で高い光吸収と光電場増強効果を示す構造が得られた。この構造に蛍光分子であるEosin Yを成膜したところ、Eosin YのOH伸縮振動と赤外モード強結合が強い相互作用を示し、蛍光寿命が赤外波長における光電場増強の大きさとともに顕著に且つ系統的に短くなること、そして解析の結果、赤外振動モードと光場の相互作用により無放射失活が大きくなることが示され、高次の電子状態に強く影響を及ぼすことが明らかとなった。

Research Progress Status

平成30年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

平成30年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] Rice University(米国)
• [Int'l Joint Research] Peking University/Harbin Institute of Technology/Nankai Universit(中国)
• [Int'l Joint Research] Ntional Chiao Tung University/Academia Sinica(台湾)
• [Int'l Joint Research] National Chiao Tung University/Academia Sinica/National Taiwan University(台湾)
• [Int'l Joint Research] Peking University(中国)
• [Int'l Joint Research] Konstanz University(ドイツ)
• [Journal Article] Exotic Mode Suppression in Plasmonic Heterotrimer System (2019)
  • Author(s): H. Song, Q. Sun, J. Li, F. Yang, J. Yang, Y. Li, K. Ueno, Q. Gong, and H. Misawa
  • Journal Title: J. Phys. Chem. C Volume: 123 Issue: 2 Pages: 1398-1405
  • DOI: 10.1021/acs.jpcc.8b10263
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Control of plasmon dephasing time using stacked nanogap gold structures forstrong near-field enhancement (2019)
  • Author(s): Kosei Ueno, Jinghuan Yang, Quan Sun, Daisuke Aoyo, Han Yu, Tomoya Oshikiri, Atsushi Kubo, Yasutaka Matsuo, Qihuang Gong, Hiroaki Misawa
  • Journal Title: Applied Materials Toaday Volume: 14 Pages: 159-165
  • DOI: 10.1016/j.apmt.2018.12.004
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Formation of Nanostructure-Controlled Strong Coupling of Porphyrin Molecules and Silver Nanoparticles Using Layered Silicates (2019)
  • Author(s): M. Eguchi, J. Li, K. Ueno, H. Misawa
  • Journal Title: Chem. Lett. Volume: 48 Issue: 3 Pages: 211-214
  • DOI: 10.1246/cl.180925
  • NAID: 130007607546
  • Peer Reviewed
• [Journal Article] Bacterial concentration detection using a PCB-based contactless conductivity sensor (2019)
  • Author(s): X.-Y. Zhang, Z.-Y. Li, Y. Zhang, X.-Q. Zang, K. Ueno, H. Misawa, K. Sun
  • Journal Title: Micromachines Volume: 10 Issue: 1 Pages: 55-55
  • DOI: 10.3390/mi10010055
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Twisted Surface Plasmons with Spin-Controlled Gold Surfaces (2019)
  • Author(s): Tsai Wei-Yi、Sun Quan、Hu Guangwei、Wu Pin Chieh、Lin Ren Jie、Qiu Cheng-Wei、Ueno Kosei、Misawa Hiroaki、Tsai Din Ping
  • Journal Title: Advanced Optical Materials Volume: 7 Issue: 8
  • DOI: 10.1002/adom.201801060
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Plasmon-assisted polarity switching of a photoelectric conversion device by UV and visible light irradiation (2018)
  • Author(s): K. Nakamura, T. Oshikiri, K. Ueno, T. Katase, H. Ohta, H. Misawa
  • Journal Title: J. Phys. Chem. C Volume: 122 Issue: 25 Pages: 14064-14071
  • DOI: 10.1021/acs.jpcc.8b01198
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Enhanced water splitting under modal strong coupling conditions (2018)
  • Author(s): X. Shi, K. Ueno, T. Oshikiri, Q. Sun, K. Sasaki, H. Misawa
  • Journal Title: Nature Nanotechnol. Volume: 13 Issue: 10 Pages: 953-958
  • DOI: 10.1038/s41565-018-0208-x
  • Peer Reviewed
• [Journal Article] Optical characterization of gold nanoblock dimers: from capacitive coupling to charge transfer Plasmons and rod modes (2018)
  • Author(s): M.-N. Su, Q. Sun, K. Ueno, W.-S. Chang, H. Misawa
  • Journal Title: J. Phys. Chem. C Volume: 122 Issue: 31 Pages: 18005-18011
  • DOI: 10.1021/acs.jpcc.8b05755
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Ultrabroad and angle tunable THz filter based on multiplexed metallic bar resonators (2018)
  • Author(s): W. Liu, Z. Dai, J. Yang, Q. Sun, C. Gong, N. Zhang, K. Ueno, H. Misawa
  • Journal Title: IEEE Photon. Technol. Lett. Volume: 30 Issue: 24 Pages: 2103-2106
  • DOI: 10.1109/lpt.2018.2877964
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Manipulation of the dephasing time by strong coupling between localized and propagating surface plasmon modes (2018)
  • Author(s): J. Yang, Q. Sun, K. Ueno, X. Shi, T. Oshikiri, H. Misawa, Q. Gong
  • Journal Title: Nat. Commun. Volume: 9 Issue: 1 Pages: 4858-4858
  • DOI: 10.1038/s41467-018-07356-x
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] 局在表面プラズモン共鳴を用いた人工光合成 (2018)
  • Author(s): 押切友也、上野貢生、三澤弘明
  • Journal Title: 触媒 Volume: 60 Pages: 140-145
• [Journal Article] 局在型および伝播型表面プラズモン共鳴励起に基づくホットエレクトロンの放出制御 (2018)
  • Author(s): 上野貢生
  • Journal Title: 光学 Volume: 47 Pages: 239-239
• [Journal Article] Solid-state plasmonic solar cells (2018)
  • Author(s): K. Ueno, T. Oshikiri, Q. Sun, X. Shi, H. Misawa
  • Journal Title: Chemical Reviews Volume: 118 Issue: 6 Pages: 2955-2993
  • DOI: 10.1021/acs.chemrev.7b00235
  • Peer Reviewed
• [Journal Article] Spatial evolution of the near-field distribution on planar gold nanoparticles with the excitation wavelength across dipole and quadrupole modes (2017)
  • Author(s): J. Yang, Q. Sun, H. Yu, K. Ueno, H. Misawa, Q. Gong
  • Journal Title: Photon. Res. Volume: 5 Issue: 3 Pages: 187-193
  • DOI: 10.1364/prj.5.000187
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Optimization of a compact layer of TiO2 via atomiclayer deposition for high-performance perovskite solar cells (2017)
  • Author(s): A. E. Shalan, S. Narra, T. Oshikiri, K. Ueno, X. Shi, H.-P. Wu, M. M. Elshanawany, E. W.-G. Diau, H. Misawa
  • Journal Title: Sustainable Energy & Fuels Volume: 1 Issue: 7 Pages: 1533-1540
  • DOI: 10.1039/c7se00220c
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Exploring the near-field of strongly coupled waveguide-plasmon modes by plasmon-induced photocurrent generation using a gold nanograting-loaded titanium dioxide photoelectrode (2017)
  • Author(s): J. Guo, K. Ueno, J. Yang, X. Shi, J, Li, Q. Sun, T. Oshikiri, H. Misawa
  • Journal Title: The Journal of Physical Chemistry C Volume: 121 Issue: 39 Pages: 21627-21633
  • DOI: 10.1021/acs.jpcc.7b07707
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Interplay of hot electrons from localized and propagating plasmons (2017)
  • Author(s): C. V. Hoang, K. Hayashi, Y. Ito, N. Gorai, G. Allison, X. Shi, Q. Sun, Z. Cheng, K. Ueno, K. Goda, .H. Misawa
  • Journal Title: Nature Communications Volume: 8 Issue: 1 Pages: 771-771
  • DOI: 10.1038/s41467-017-00815-x
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Enhancing surface sensitivity of nanostructure-based aluminum sensors using capped dielectric layers (2017)
  • Author(s): K.-L. Lee, P.-G. Tsai, M.-L. You, M.-Y. Pan, X. Shi, K. Ueno, H. Misawa, P.-K. Wei
  • Journal Title: ACS Omega Volume: 2 Issue: 10 Pages: 7461-7470
  • DOI: 10.1021/acsomega.7b01349
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] 局在プラズモンの人工光合成への展開 (2017)
  • Author(s): 押切 友也, 上野 貢生, 三澤 弘明
  • Journal Title: 月刊機能材料 Volume: 37 Pages: 40-49
• [Journal Article] Foundation of Localized Surface Plasmon and its Application to Photochemical Reactions (2017)
  • Author(s): 押切 友也, 上野 貢生, 三澤 弘明
  • Journal Title: Journal of the Japan Society of Colour Material Volume: 90 Issue: 12 Pages: 408-413
  • DOI: 10.4011/shikizai.90.408
  • NAID: 130006301986
  • ISSN: 0010-180X, 1883-2199
• [Presentation] Plasmon-induced photocurrent generation for exploring the near-field of strongly coupled plasmonic systems (2018)
  • Author(s): Ueno Kosei、Guo Jingchun、Shi Xu、Oshikiri Tomoya、Misawa Hiroaki
  • Organizer: 233rd ECS meeting
  • Int'l Joint Research / Invited
• [Presentation] Spectral properties of plasmonic strong coupling systems (2018)
  • Author(s): Ueno Kosei、Sun Quan、Misawa Hiroaki
  • Organizer: The international Symposium On Plasmonics and Nano-photonics (iSPN2018)
  • Int'l Joint Research / Invited
• [Presentation] Near-field spectral properties of nano-engineered metallic nanoparticles (2018)
  • Author(s): Ueno Kosei、Sun Quan、Misawa Hiroaki
  • Organizer: OSA Advanced Photonics Congress 2018
  • Int'l Joint Research / Invited
• [Presentation] Near-field spectral properties of metal/insulator/metal nanostructures showing quadrupole plasmon mode (2018)
  • Author(s): Ueno Kosei、Yang Jinghuan、Tatsumi Ryota、Sun Quan、Oshikiri Tomoya、Misawa Hiroaki
  • Organizer: The 12th International Conference on Excitonic and Photonic Processes in Condensed Matter and Nano Materials (EXCON 2018)
  • Int'l Joint Research
• [Presentation] Near-field spectral properties of the coupled plasmonic systems (2018)
  • Author(s): Ueno Kosei、Sun Quan、Shi Xu、Oshikiri Tomoya、Misawa Hiroaki
  • Organizer: Asia Pacific Society for Materials Research (APSMR2018)
  • Int'l Joint Research / Invited
• [Presentation] Spectral properties of dye molecules in infrared plasmon-cavity strong coupling systems (2018)
  • Author(s): Ueno Kosei、Shi Xu、Sun Quan、Oshikiri Tomoya、Misawa Hiroaki
  • Organizer: 2018年光化学討論会
• [Presentation] プラズモン－ナノ共振器強結合による広帯域光吸収体の構築と光エネルギー変換系への展開 (2018)
  • Author(s): 上野貢生、石 旭、孫 泉、押切友也、笹木敬司、三澤弘明
  • Organizer: 第67回高分子討論会
  • Invited
• [Presentation] Construction of visible responsive broadband absorber utilizing strong coupling between plasmon and nanocavity modes and its application to light energy conversions (2018)
  • Author(s): Ueno Kosei、Shi Xu、Sun Quan、Oshikiri Tomoya、Sasaki Keiji、Misawa Hiroaki
  • Organizer: The 79th JSAP Autumn Meeting, JSAP-OSA Joint Symposia
  • Int'l Joint Research / Invited
• [Presentation] Fluorescence properties of organic dye in infrared plasmon-cavity strong coupling (2018)
  • Author(s): Ueno Kosei、Shi Xu、Sun Quan、Oshikiri Tomoya、Misawa Hiroaki
  • Organizer: 10th Asian Photochemistry Conference (APC2018)
  • Int'l Joint Research / Invited
• [Presentation] Modal strong coupling for versatile surface-enhanced Raman scattering chips (2018)
  • Author(s): Zang Xiaoqian、Shi Xu、Oshikiri Tomoya、Ueno Kosei, Misawa Hiroaki
  • Organizer: 10th Asian Photochemistry Conference (APC2018)
  • Int'l Joint Research
• [Presentation] 金属／誘電体／金属ナノ構造の近接場分光特性 (2018)
  • Author(s): 上野貢生、Yang Jinghuan、巽 亮太、孫 泉、押切友也、三澤弘明
  • Organizer: 第66回応用物理学会春季学術講演会
• [Presentation] 局在プラズモン－ナノ共振器強結合場における蛍光分子の発光特性 (2018)
  • Author(s): 大西 梓、Zu Shuai、石 旭、孫 泉、押切友也、上野貢生、三澤弘明
  • Organizer: 第66回応用物理学会春季学術講演会
• [Presentation] Dynamics of electron transfer in gold nanoparticles/titanium dioxide system by transient absorption spectroscopy (2018)
  • Author(s): J. Li, K. Ueno, Q. Sun, T. Oshikiri, H. Misawa
  • Organizer: 日本化学会 第98春季年会 (2018)
• [Presentation] 3次元プラズモン光アノードの金属/半導体界面制御 (2018)
  • Author(s): 高倉 稜平, 押切 友也, 上野 貢生, 近藤 敏彰, 益田 秀樹, 三澤 弘明
  • Organizer: 日本化学会 第98春季年会 (2018)
• [Presentation] Fabrication of high-absorption plasmonic photoanode with microhole array (2018)
  • Author(s): T. Oshikiri, K. Ueno, H. Misawa
  • Organizer: 日本化学会 第98春季年会 (2018)
• [Presentation] ファブリ・ペローナノ共振器-プラズモン強結合を利用した高光吸収太陽電池の電気特性評価 (2018)
  • Author(s): 中村 圭佑, 押切 友也, 石 旭, 上野 貢生, 三澤 弘明
  • Organizer: 日本化学会 第98春季年会 (2018)
• [Presentation] Strong coupling between Fabry-Perot nanocavity and localized surface plasmon resonance and its application for efficient water splitting (2018)
  • Author(s): X. Shi, K. Ueno, T. Oshikiri, Q. Sun, K. Sasaki, H. Misawa
  • Organizer: 日本化学会 第98春季年会 (2018)
• [Presentation] Spectral properties of the strong coupling between microcavity and molecular vibrational modes (2018)
  • Author(s): K. Ueno, T. Oshikiri, H. Misawa
  • Organizer: 日本化学会 第98春季年会 (2018)
• [Presentation] Plasmonic nanoparticles and the coherent interaction with dye molecules (2018)
  • Author(s): M. Eguchi, K. Ueno, H. Misawa
  • Organizer: 日本化学会 第98春季年会 (2018)
• [Presentation] Near-field spectral properties of coupled plasmonic systems (2017)
  • Author(s): K. Ueno, Q. Sun, H. Misawa
  • Organizer: Progress In Electromagnetics Research Symposium 2017 (PIERS 2017)
  • Int'l Joint Research / Invited
• [Presentation] Near-field spectroscopy of the coupled plasmonic systems using multiphoton photoemission electron microscopy (2017)
  • Author(s): K. Ueno, Q. Sun, H. Misawa
  • Organizer: 9th International Conference on Materials for Advanced Technologies (ICMAT2017)
  • Int'l Joint Research / Invited
• [Presentation] プラズモニックナノ構造の作製と近接場分光特性 (2017)
  • Author(s): 上野 貢生
  • Organizer: 名古屋大学 応用物質化学セミナー
  • Invited
• [Presentation] プラズモン放射圧による高分子ゲルの体積相転移 (2017)
  • Author(s): 上野 貢生
  • Organizer: 分子研研究会「共鳴条件下における光と分子の力学的相互作用 -分子操作への展開-」
  • Invited
• [Presentation] Quantitative evaluation of plasmon-induced ammonia photoelectrochemical synthesis (2017)
  • Author(s): T. Oshikiri, K. Ueno, H. Misawa
  • Organizer: International Conference on Photochemistry 2017 (ICP2017)
  • Int'l Joint Research
• [Presentation] Spectral properties and dynamics of localized surface plasmon resonances in metal/insulator/metal nanostructures (2017)
  • Author(s): K. Ueno, J. Yang, H. Yu, Q. Sun, T. Oshikiri, A. Kubo, Y. Matsuo, Q.-H. Gong, H. Misawa
  • Organizer: International Conference on Photochemistry 2017 (ICP2017)
  • Int'l Joint Research
• [Presentation] 金ナノ粒子を担持した3 次元プラズモン光アノードの構造・光エネルギー変換特性評価 (2017)
  • Author(s): 高倉 稜平, 押切 友也, 近藤 敏彰, 上野 貢生, 益田 秀樹, 三澤 弘明
  • Organizer: 2017年光化学討論会
• [Presentation] Spectral modulations of molecular vibrational modes by infrared localized surface plasmon resonance (2017)
  • Author(s): K. Ueno, J. Li, T. Oshikiri, H. Misawa
  • Organizer: 2017年光化学討論会
• [Presentation] Near-field spectral properties and ultrafast dynamics (2017)
  • Author(s): J. Yang, Q. Sun, H. Yu, K. Ueno, Q. Gong, H. Misawa
  • Organizer: 2017年光化学討論会
• [Presentation] 局在プラズモンとマイクロキャビティとのカップリングを用いた高光吸収プラズモン太陽電池の構築 (2017)
  • Author(s): 中村 圭佑, 押切 友也, 石 旭, 上野 貢生, 三澤 弘明
  • Organizer: 2017年光化学討論会
• [Presentation] アキラル構造における近接場キラリティーの観測 (2017)
  • Author(s): 山田 拓樹, 押切 友也, 孫 泉, 上野 貢生, 三澤 弘明
  • Organizer: 2017年光化学討論会
• [Presentation] Reaction mechanism on plasmon-induced ammonia synthesis (2017)
  • Author(s): T. Oshikiri, K. Ueno, H. Misawa
  • Organizer: 2017年光化学討論会
• [Presentation] プラズモニックナノ構造の近接場分光特性と光化学研究への展開 (2017)
  • Author(s): 上野 貢生
  • Organizer: 東工大化学系セミナー
  • Invited
• [Book] プラズモンの化学 (2019)
  • Author(s): 上野 貢生、三澤 弘明
  • Total Pages: 122
  • Publisher: 共立出版
  • ISBN: 9784320044708
• [Book] プラズモンと光圧が導くナノ物質科学 (2019)
  • Author(s): 上野貢生、押切友也
  • Total Pages: 10
  • Publisher: 化学同人
  • ISBN: 9784759813920
• [Book] Handbook of Solid State Chemistry, Vol. 2 (2017)
  • Author(s): K. Ueno, H. Misawa
  • Publisher: Wiley-VCH Verlag GmbH
  • ISBN: 9783527325870
• [Remarks] http://www.kueno.com/
• [Patent(Industrial Property Rights)] 電気測定型表面プラズモン共鳴センサ及びそれに用いる電気測定型表面プラズモン共鳴センサチップ (2018)
  • Inventor(s): 鈴木博紀、Allison Giles、三澤弘明、上野貢生他
  • Industrial Property Rights Holder: イムラジャパン（株）・北海道大学
  • Industrial Property Rights Type: 特許
  • Filing Date: 2018
  • Overseas
• [Patent(Industrial Property Rights)] 電気測定型表面プラズモン共鳴センサ及びそれに用いる電気測定型表面プラズモン共鳴セ ンサチップ (2017)
  • Inventor(s): 鈴木博紀, 林弘毅, 上野貢生, 三澤弘明, 他2名
  • Industrial Property Rights Holder: イムラジャパン株式会社, 国立大学法人 北海道大学
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2017-155187
  • Filing Date: 2017
• [Patent(Industrial Property Rights)] 光吸収デバイスおよびその製造方法ならびに光電極 (2017)
  • Inventor(s): 三澤弘明, 石旭, 上野貢生, 押切友也, 孫泉, 笹木敬司
  • Industrial Property Rights Holder: 国立大学法人 北海道大学
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2017-248071
  • Filing Date: 2017